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QUANTUM THEORY
OUTLINE
SECT TOPIC
1. Which of the following functions are normalizable over the indicated intervals?
Normalize those functions which can be normalized.
(a) exp(-ax2) (-,); (b) ex (0,); (c) ei (0,2); (d) xe-3x (0,)
4. True or False
(a) Nondegenerate eigenfunctions of the same operaor are orthogonal.
(b) All Hermitian operators are real.
(c) If two operators commute with a third, they will commute with each other.
(d) d/dx must be continuous as long as the potential, V(x), is finite.
(e) If a wavefunction is simultaneously the eigenfunction of two operators, it will
also be an eigenfuncion of the product of the two operators.
d d
7. Calculate the commutator: , x
dx dx
DATA
h = 6.63x10-34 Js 1 J = 1 kgm2/s2
= h/2 = 1.05x10-34 Js 1 = 10-10 m
c = 3.00x108 m/s = 3.00x1010 cm/s kNA = R
NA = 6.02x1023 mol-1 1 amu = 1.66x10-27 kg
k = 1.38x10-23 J/K 1 atm. = 1.013x105 Pa
R = 8.31 J/mol-K 1 eV = 1.60x10-19 J
R = 8.31 Pa-m3/mol-K
me = 9.11x10-31 kg (electron mass)
2
e x dx
0 2
n!
0
x n e ax dx
a n 1
d2
p 2 (oper ) 2
dx 2
Linear operators
Wavefunction orthogonality
Linear combinations of degenerate wavefunctions
Quantum Theory
Slide 1
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
1
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 3
One Dimension
x x+dx
Slide 4
2
Three Dimensions
z Shorthand Notation
dz
dy y
dx
Two Particles
Slide 5
Required Properties of
Finite X
Continuous (x)
3
Required Properties of
Vanish at endpoints 0 as x
(or infinity) y
z
or
Shorthand notation
Slide 7
OK
No - Diverges as x -
No - Multivalued
i.e. x = 1, sin-1(1) = /2, /2 + 2, ...
Slide 8
4
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 9
5
Linear Operators
A quantum mechanical operator must be linear
Operator Linear ?
x2 Yes
No
log No
sin No
Yes
Yes
Slide 11
Operator Multiplication
^ ^
First operate with B, and then operate on the result with A.
Note:
Example
Slide 12
6
Operator Commutation
?
Slide 13
Eigenvalue Equations
f Eigenfunction? Eigenvalue
3 x2 Yes 3
x sin(x) No
sin(x) No
Slide 14
7
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 15
Slide 16
8
Derivation of the momentum operator
Wavefunction for a free particle (from Chap. 1)
where
Slide 17
Momentum px (or p)
Kinetic Energy
Total Energy
Slide 18
9
Some Important Operators (3 Dim.) in QM
Momentum
Kinetic Energy
Total Energy
Slide 19
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 20
10
The Schrdinger Equation (One Dim.)
Postulate 3: The wavefunction, (x,t), is obtained by solving the
time dependent Schrdinger Equation:
Slide 21
On Board
Slide 22
11
= E (the energy, a constant)
On Board
Time Independent
Schrdinger Equation
Slide 23
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 24
12
Math Preliminary: Probability, Averages & Variance
Probability
x x+dx
Slide 25
Positional Averages
Discrete Distribution:
Continuous Distribution:
Slide 26
13
Continuous Distribution:
If normalized If normalized
Slide 27
Variance
Below is a formal derivation of the expression for Standard Deviation.
This is FYI only.
14
Example
P(x) = Ax 0x10 Calculate: A , <x> , <x2> , x
P(x) = 0 x<0 , x>10
Note:
Slide 29
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 30
15
Normalization of the Wavefunction
Slide 31
A Wavefunction:
Slide 32
16
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 33
Slide 34
17
Find the value of A that normalizes the Harmonic Oscillator
oscillator wavefunction:
Slide 35
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 36
18
Eigenfunctions and Eigenvalues
Postulate 4: If a is an eigenfunction of the operator with
eigenvalue a, then if we measure the property A for
a system whose wavefunction is a, we always get
a as the result.
Example
The operator for the total energy of a system is the Hamiltonian.
Show that the HO wavefunction given earlier is an eigenfunction
of the HO Hamiltonian. What is the eigenvalue (i.e. the energy)
Slide 37
Slide 38
19
To end up with a constant times ,
this term must be zero.
Slide 39
E = = h
Because the wavefunction is an
eigenfunction of the Hamiltonian,
the total energy of the system
is known exactly.
Slide 40
20
Is this wavefunction an eigenfunction of the potential energy operator?
Slide 41
21
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 43
Expectation Values
Postulate 5: The average (or expectation) value of an observable
with the operator is given by
If is normalized
Slide 44
22
Expectation value of the position
Slide 45
x2 p2 <PE>
Slide 46
23
Preliminary: Wavefunction Derivatives
Slide 47
<x>
<x2>
Also:
Slide 48
24
<p>
Slide 49
<p2>
Also:
Slide 50
25
Uncertainty Principle
Slide 51
<KE>
<PE>
Slide 52
26
Consider the HO wavefunction we have been using in
earlier examples:
<x> = 0 <p> = 0
x2 = 1/(2) p2 = 2/2
<PE> = = h
Slide 53
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 54
27
Hermitian Operators
General
Definition: An operator is Hermitian if it satisfies the relation:
Simplified
Definition (=): An operator is Hermitian if it satisfies the relation:
So what?
Why is it important that a quantum mechanical operator be Hermitian?
Slide 55
Proof: and
a* = a
i.e. a is real
28
Is the operator x (multiplication by x) Hermitian? Yes.
Slide 57
?
The question is whether:
?
or:
Slide 58
29
?
?
or:
Let u = and v = *:
Because and *
vanish at x =
?
Therefore:
Slide 59
IS Hermitian
Slide 60
30
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 61
Orthogonality of Eigenfunctions
Slide 62
31
Thus, if Ei Ej (i.e. the eigenfunctions are not degenerate,
then:
Slide 63
Proof:
If Ej = Ei ,
32
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 65
Commutation of Operators
?
Slide 66
33
x x2 0 Operators commute
3 0 Operators commute
And so??
Why does it matter whether or not two operators commute?
Slide 67
34
We just showed that the momentum and position operators do not
commute:
Slide 69
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 70
35
Differentiability and Completeness
of the Wavefunction
Differentiability of
It is proven in in various texts** that the first derivative of the
wavefunction, d/dx, must be continuous.
x
The one exception to the continuous derivative requirement is
if V(x).
We will see that this property is useful when setting Boundary
Conditions for a particle in a box with a finite potential barrier.
** e.g. Introduction to Quantum Mechanics in Chemistry, M. A. Ratner
and G. C. Schatz, Sect. 2.7
Slide 71
This means that any well behaved function defined over the
same interval (i.e. - to for a Harmonic Oscillator,
0 to a for a particle in a box, ...) can be written as a linear combination
of the eigenfunctions; i.e.
Slide 72
36
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 73
In this notation:
Slide 74
37
In Bra-Ket notation, we have the following:
Scalar Product
of two functions:
Orthogonality:
Normalization:
Hermitian
Operators:
Expectation
Value:
Slide 75
38